Water-repellent and soil-resistant finish for textiles

ABSTRACT

The present invention is directed to polymeric treatment preparations for textiles and other fibrous substrates that impart water and oil repellency to fibers, yarns, textiles, or other fibrous substrates. More particularly, this invention comprises an aqueous solution, emulsion or suspension of (a) a fluorinated polymer that contains reactive groups that can complex with metal atoms that have a formal charge of 2 or greater, and (b) one or more metal atoms that have a formal charge of 2 or greater. The invention is further directed to the process for treating fibrous substrates with textile preparations in one step that provide water/soil repellency that is durable to repeated cleanings and to abrasion. This invention is further directed to the yarns, fibers, fabrics, textiles, webs, finished goods, or nonwovens (encompassed herein under the terms “textiles” and “fibrous substrates”) treated with the textile-reactive water- and soil-resistant preparation of the invention. Such fibrous substrates exhibit a greatly improved, durable water and soil repellency or resistance, even after multiple launderings.

The present invention is a continuation-in-part of co-pendingInternational Patent Appln. No. PCT/US00/24691, filed Sep. 8, 2000 anddesignating the United States of America, which application claims thebenefit of Provisional U.S. application Ser. No. 60/153,393, filed Sep.10, 1999 and of Provisional U.S. application Ser. No. 60/176,949, filedJan. 18, 2000; the entire disclosures of all of which are incorporatedherein by reference.

FIELD OF THE INVENTION

The present invention relates to textile treatment compositions forimparting water/soil resistance to fibrous substrates, includingtextiles.

BACKGROUND OF THE INVENTION

Two methods of imparting hydrophobic character to textiles have beeninvestigated in the past: 1) hydrophobic polymer films, and 2)attachment of hydrophobic monomers and polymers via physi- orchemisorptive processes.

Current commercial processes for producingwater-repellent/soil-resistant fabrics are mainly based on thelaminating processes of companies such as W. L. Gore and Sympatex(Journal of Coated Fabrics vol. 26, 1996, pp. 107-130) and polysiloxanecoatings (Handbook of Fiber Science and Technology, Marcel Dekker, NewYork, N.Y., Vol. II, 1984, pp. 168-171). The laminating process involvesadhering a layer of polymeric material (such as Teflon™ that has beenstretched to produce micropores) to a fabric. Although this processproduces durable repellent films, it suffers from many disadvantages.The application of these laminants requires special equipment andtherefore cannot be applied using existing textile production processes.Synthesis of the film is costly and garments with this modification aresignificantly more expensive than their unmodified counterparts. Thecolors and shades of this clothing are limited by the coating color.Finally, clothing made from this material tends to be heavy and stiff.Polysiloxane films suffer from low durability to laundering, which tendsto swell the fabric and rupture the silicone film. The polysiloxaneshave a cost advantage over the laminates, which are, however, moredurable to laundering and dry-cleaning.

Repellents based on monomeric hydrocarbon hydrophobes can be broken downinto five categories: 1) aluminum and zirconium soaps, 2) waxes andwaxlike substances, 3) metal complexes, 4) pyridinium compounds, 5)methylol compounds, and 6) other fiber-reactive water repellents.Compared to polymeric coatings, monomeric hydrophobes can penetratewithin the fabric to produce a more durable coating.

One of the oldest water repellents was based on non-covalently applyingwater-soluble soap to the fibers and precipitating it with an aluminumsalt (J. Text. Res. vol. 42, 1951, p. 691). These coatings dissolved inalkaline detergent solution, therefore washfastness was poor. Zirconiumsoaps were less soluble in detergent solutions (Waterproofing andWater-Repellency, Elsevier Publ. Co., Amsterdam, 1963, p. 188), but dueto the noncovalent nature of attachment to the fabric, abrasionresistance was poor.

The oldest and most economical way to make fabric water repellent is tocoat it with a hydrophobic substance, such as paraffin (Text. Inst. Ind.vol. 4, 1966, p. 255). This process is still in practice today andparaffin emulsions for coating fabrics can be purchased (e.g., Freepel®from BFGoodrich Textile Chemicals, Inc.). Waxes are not stable tolaundering or dry cleaning. Durability is poor due to their noncovalentnature of binding and their breathability is low.

Quilon chrome complexes polymerize to form —Cr—O—Cr— linkages (Tappivol. 36, 1953, p. 107). Simultaneously, the complex forms covalent bondswith the surface of fibers with hydrophobic chains directed away fromthe surface to produce a water repellent, semi-durable coating. Quilonsolutions require acidic conditions to react, thus causing degradationof the cellulose fibers through cellulose hydrolysis. Fabric colors arelimited by the blue-green coloration imparted by the metal complex.

The extensive history of pyridinium-type water repellents has beenreviewed by Harding (J. Text. Res. vol. 42, 1951, p. 691). In essence,an alkyl quaternary ammonium compound is reacted with cellulose atelevated temperatures to form a durable water-repellent finish on cotton(Br. Pat. 466,817) and a later version was marketed under the trademarkVelan PF by ICI. It was later found that the reaction was restricted tothe surface of the fibers (J. Soc. Dyers Colour. vol. 63, 1947, p. 260)and the high cure temperature weakened the fabric. Sodium acetate had tobe added to prevent the decomposition of the cellulose by the HClformed. Also, the pyridine liberated during the reaction has anunpleasant odor and the fabric had to be scoured after the cure. Thetoxicological properties of pyridine ended its use in the 1970s whengovernment regulations on such substances increased.

Methylol chemistry has been extensively commercialized in thecrosslinking of cellulose for durable press fabrics. N-methylolcompounds are prepared by reaction of an amine or amide withformaldehyde. Alkyl-N-methylol compounds can be reacted at elevatedtemperatures in the presence of an acidic catalyst with the hydroxylgroups of textiles to impart durable hydrophobic qualities (Br. Pats.463,300 and 679,811). The reaction is accompanied by formation ofnon-covalently linked (i.e., non-durable) resinous material, thusdecreasing efficiency. In addition, the high temperature and acidcatalyst reduce the strength of the fabric. Recently, the commercial useof methylol compounds has been waning due to concerns of toxicformaldehyde release from fabrics treated in such a manner.

Several other chemical reactions have been used to covalently attachhydrophobic species to cotton to produce a water-repellent finish buthave not been commercialized for various reasons. Long-chain isocyanateshave been used in this respect (Br. Pat. 461,179; Am. Dyest Rep. vol.43,1954, p. 453; Br. Pat. 474,403). The high toxicity of isocyanates andsignificant side reactions with water, however, precluded it fromcommercial use. To circumvent the water sensitivity of isocyanates,alkyl isocyanates were reacted with ethylenimine to yield the lessreactive aziridinyl compound, which was subsequently reacted withcellulose at 150° C. (Ger. Pat. 731,667; Br. Pat. 795,380). Although thetoxicity of the aziridinyl compound was reduced compared to theisocyanate, the procedure still required the handling of toxicisocyanate precursors. Also, the high cure temperature weakened thecellulose, and crosslinkers were needed to increase structuralstability. Alkyl epoxides can be reacted with cellulose under acidic orbasic conditions to produce durable, water-repellent cotton (Ger. Pat.874,289). The epoxide was applied from a volatile solvent to suppressside reactions with water. Epoxides are, in general, not very reactive,thus requiring long reaction times at high temperatures. Therefore, theyhave not been commercialized. Acylation of cotton with isopropenylstearate from an acidic solution of benzene and curing at 200° C.produced a durable hydrophobic coating (U.S. Pat. No. 4,152,115). Thehigh cure temperature and acid catalyst again weakened the cotton.Carcinogenic benzene can be replaced by toluene, but the practicality ofusing flammable solvents in fabric finishing is limited. Alkyl vinylsulfones react with cellulose in the presence of alkali to form arepellent finish (U.S. Pat. No. 2,670,265). However, this method has notbeen commercialized because the alkali is not compatible withcross-linking reactants required for permanent press treatments.

Recently, copolymers containing a fluorinated monomer, an alkyl monomer,a reactive monomer (e.g., hydroxyethylmethacrylate, N-methylolacrylamide), and various other auxiliary monomers (e.g. vinylidenechloride, polyethylene glycol methacrylate, etc.) have become popularcommercial products for the aqueous application of somewhat durablewater and oil repellent finish to textiles (e.g., Zonyl™ by DuPont,Nuva™ by Clariant, and Scotchgard™ by 3M). These polymers, however,suffer from the release of formaldehyde from the treated fabric due tothe breakdown of the N-methlyol acrylamide portion of the copolymer.

The use of mordants (insoluble metal complexes) have been used topermanently attach fluorinated compounds (containing groups such asacids capable of forming insoluble complexes with the mordant metal) toa textile substrate. The mordant approach of attaching the fluorinatedcompound to the substrate eliminates the use of theformaldehyde-releasing components described above. U.S. Pat. No.3,651,105 uses a solvent-soluble fluorinated metal complex that isapplied to paper and fabric. This complex is monomeric, so it only hasone point of attachment as opposed to multiple attachment pointsafforded by a polymer. But, more importantly, this complex is onlysoluble in a carbon tetrachloride/isopropanol mixture. The use of toxicand flammable solvents in a textile process is impractical.Water-soluble complexes are preferred. U.S. Pat. No. 3,467,612 uses awater-soluble fluoropolymer/metal complex but the fluoropolymer does notcontain any monomers capable of complexing with a divalent metal tobridge to a substrate. However, although the fluorinated complex isinsolubilized on the fabric, it is not directly bound to a group on thesubstrate; thus durability to abrasion is low. Other patents usingdivalent metals use a two-step process where the metal is applied to thefabric first and then the fluoropolymer containing a monomer capable ofcomplexing a divalent metal is applied to the fabric in a second step.EP 0710738 teaches a two-step process: application of a divalent metalfollowed by application of a random fluoro-copolymer (containingmonomers capable of binding the divalent metal). The use of two stepsgreatly decreases the utility of this approach due to cost issues. U.S.Pat. No. 5,744201 uses a water-soluble random fluoro-copolymer with anacid-containing monomer that is rendered insoluble (and thusprecipitated on the fabric) by changing the pH in the presence ofammonium ion (single valent). The copolymer and the ammonium ion form aninsoluble complex at a specific pH and is not directly bound to a groupon the substrate; thus durability to abrasion is low. EP 572269A1 issimilar except for the use a polyallylamine salt instead of ammonium.This patent also mentions the use of monomeric fluorinated zirconiumcompounds as additives to boost performance. U.S. Pat. No. 4,695,488incorporates acrylic acid in their fluoropolymer to increase soilrelease properties but do not use this acid group to form insolubledivalent salt linkages to the fabric substrate. The purpose of the acidgroups is to increase the soil-release properties of the finish.

SUMMARY OF THE INVENTION

This invention is directed to treatment preparations useful for thetreatment of fibrous substrates, such as textiles and other webs, toprovide substantially permanent, durable water and soil repellency tokeratinous and/or cellulosic fibrous substrates. More particularly, theinvention is directed to preparations that comprise a fluorinatedpolymer and metal atoms, typically as a metal salt. The claimedfluorinated copolymer incorporates the divalent metal salt but is stillwater-soluble (because of water-soluble monomers in the polymer andsurfactants), allowing for a one-step application of both thefluoropolymer and metal. The divalent metal will complex with groups onthe fabric to make an insoluble complex on the fabric that is directlybound to the substrate of the fabric for increased abrasion durability.Furthermore, the claimed fluorinated copolymer is a block copolymer inwhich the polymer has long stretches of only fluoromonomer and longstretches of monomers capable of complexing divalent metals. Thisincreases the water solubility of the polymer of the present inventionand increases the strength with which the polymer binds to the fiberthrough a divalent metal.

In a first embodiment, the preparations of the invention comprise (a) afluorinated carboxylate-functionalized fluoropolymer and (b) a metalsalt, or mordant.

In a second embodiment, this invention comprises a solution, emulsion orsuspension of (a) a fluorinated polymer that contains functionalmoieties or reactive groups that can complex with metal atoms that havea formal charge of 2 or greater, and (b) one or more metal atoms thathave a formal charge of 2 or greater.

By “fluorinated polymer” or “fluoropolymer” is meant that the polymerwill contain some perfluorinated or partially fluorinated alkyl chainsto impart water and oil repellency to coated objects. It mayadditionally be advantageous for the polymer to contain other groupssuch as normal alkyl chains; groups that can increase the watersolubility or stability of the suspension of the polymer, such as chainsof polyethylene glycol or other polar groups; one or more differentgroups that can crosslink to each other or to the material being coated;or groups that increase polymer flexibility, flame retardancy, thesoftness of a textile, or resistance to bacteria or mildew.

The metal atoms in the solution of the second embodiment can come fromtwo sources. Either they are part of a monomer that is copolymerized tobecome part of the polymer, such as calcium, magnesium, aluminum, orchromium acrylate; or they are added in the form of a compound that hasa metal with a formal charge of 2 or greater. This addition of the metalcan take place before polymerization, during polymerization, or afterpolymerization. Without being bound by theory, it is believed that themetal atoms may complex with keratinous or any other fibrous substratesthat contain free carboxyl groups. By “complexing” is meant that thepolymer will form a coordination bond with the metal and the metal willform a coordination bond to the fiber, textile, or web to be treated.Alternatively, again without being bound by theory, the metal atoms mayact to crosslink the polymer to itself and to other chains to make thepolymer insoluble in the fibrous substrate. In either case, theresulting water/soil repellent preparation has more durable water andsoil repellency in and/or on the substrate fiber structure whileretaining the natural properties of the fibrous substrate.

This invention is further directed to a novel block copolymer containingi) one or more blocks composed primarily of acrylic acid, methacrylicacid, maleic anhydride, maleic acid, crotonic acid, itaconic acid, orother acid-containing monomers, and ii) one or more blocks that containa significant amount of a fluorinated monomer that is capable of bindingto wool or other fibrous substrates with a metal. They may furthercomprise a monomer that contains a metal, such as calcium, magnesium,aluminum, potassium, or chromium acrylates or styrene sulfonates.

This invention is further directed to the yarns, fibers, fabrics,textiles, webs, finished goods, or nonwovens (encompassed herein underthe terms “textiles” and “fibrous substrates”) treated with the water-and soil-resistant preparations of the invention. Such fibroussubstrates exhibit a greatly improved, durable water and soilrepellency. By “durable water and soil repellency” is meant that thefibrous substrate will exhibit a repellency or resistance to water andoily soils even after multiple launderings.

Methods are provided for treating fabrics and other fibrous substrateswith permanent water/soil repellent coatings.

DETAILED DESCRIPTION OF THE INVENTION

The preparations of the invention comprise a combination of metal atoms,typically as a metal salt, and a metal-reactive fluorinated polymercapable of imparting a water/soil-resistant property to textiles andother fibrous substrates. The metal imparts greater stability anddurability to the polymer when the polymer is immobilized on thesubstrate than when the metal is not present.

The fluorinated monomers, oligomers or macromonomers of the durablewater/soil-resistant fluoropolymer are selected from those groups thatwill provide the necessary water/soil resistance and can be polymerized.Examples include fluorinated monomers of acrylates, methacrylates,alkenes, alkenyl ethers, styrenes, and the like. Monomers that containcarbon-fluorine bonds that would be useful in this invention include,but are not limited to, Zonyl TA-N (an acrylate from DuPont), Zonyl TM(a methacrylate from DuPont), FX-13 (an acrylate from 3M), and FX-14 (amethacrylate from 3M). The fluoropolymers may include —CF₃ and —CHF₂ endgroups, perfluoroisopropoxy groups (—OCF(CF₃)₂), 3,3,3-trifluoropropylgroups, and the like. The polymers may include vinyl ethers havingperfluorinated or partially fluorinated alkyl chains. The fluoropolymerpreferably comprises one or more fluoroaliphatic radical-containingmonomers having the structure of Formula I, below:

In the compound of Formula I, for example:

m is 0 to 2;

n is 0 or 1;

o is 1 or 2;

A is —SO₂—, —N(W)—SO₂—, —CONH—, —CH₂—, or —CF₂—;

R is a linear, branched, or cyclic fluorocarbon, including fully orpartially fluorinated hydrocarbons, wherein R may be, for example, a C₁to C₃₀ fluorocarbon;

W is hydrogen or C₁-C₄ lower alkyl; and

X is acrylate (H₂C═CHCO₂—), methacrylate (H₂C═C(CH3)CO2-), or acarbon-carbon double bond (H₂C═CH—).

Particularly useful fluorinated monomers are acrylate and methacrylatemonomers with the structures H₂C═CHCO₂CH₂CH₂(CF₂)_(n)F andH₂C═C(CH₃)CO₂CH₂CH₂(CF₂)_(n)F, where n in both cases is 1 to 20. Morepreferably n lies between approximately 5 and 12, although mostcommercially available monomers contain a distribution of chain lengthsand a few of them may fall outside of this range.

The preferred embodiment of this invention is a fluoropolymer preparedby the emulsion process in water or in a mixture of water and an organicsolvent that is then dissolved or suspended in water or into a solutionin which water is a significant component.

The reactive groups on the water/soil-resistant fluoropolymer areselected from those groups that will coordinately bind strongly with ametal. Such moieties include, but are not limited to, carboxyl,carboxylate, sulfate, sulfonate, phosphate, and phosphonate groups. Forexample, the metal-reactive monomers may be selected from groups thatcontain carboxylates such as acrylic acid, methacrylic acid,bisacrylamidoacetic acid, 3-butene-1,2,3-tricarboxylic acid, maleicacid, 2-carboxyethyl acrylate, itaconic acid, 4-vinylbenzoic acid, andthe like; or sulfonates such as 2-acrylamido-2-methyl-1-propanesulfonicacid, 2-methyl-2-propene-1-sulfonic acid, 2-propene-1-sulfonic acid,2-sulfoethyl methacrylate, 3-sulfopropyl methacrylate, vinylsulfonicacid, styrene sulfonic acid, styrene sulfonic acid (sodium salt), andthe like; or phosphates or phosphonates such as vinyl phosphonic acid orvinyl phosphoric acid, and the like. In one embodiment of the invention,particularly useful monomers, macromonomers, oligomers, or polymers arethose that have carboxyl-containing monomers copolymerized with at leastsome fluorinated monomers or polymers.

A monomer such as styrene sulfonate or potassium acrylate may be usedwhere an additional metal atom with a formal charge of 2 or greater maybe added before, during, or after polymerization.

Ideally, the actual metal-polymer salt would be water-soluble or atleast have some water solubility. When dried properly, hydrophobicgroups in the polymer would orient themselves in such a way as to imbedor surround metal-anion complexes. When metals with a formal charge of 2or greater are used, polymer crosslinking providing added stability,could result.

The metal salt is chosen from those that form an insoluble or nearlyinsoluble complex with the polymer, especially when the polymer is driedor cured. Preferred are metal salts that also react or complex with thesurface of the fiber of the textile or web. Preferred examples of metalsalts that can be added to the polymer prior to, during or afterpolymerization include calcium (II), magnesium (II), zirconium (IV),aluminum (III), and chromium (III) salts such as calcium chloride(CaCl₂), calcium sulfate (CaSO₄), calcium nitrate (Ca(NO₃)₂), magnesiumchloride (MgCl₂), magnesium sulfate (MgSO₄), magnesium nitrate(Mg(NO₃)₂), zirconium oxychloride (ZrOCl₂), zirconium nitrate(Zr(NO₃)₄), zirconium sulfate (Zr(SO₄)₂), zirconyl nitrate (ZrO(NO₃)₂),aluminum sulfate (Al₂(SO₄)₃), aluminum potassium sulfate (alum)(AlK(SO₄)₂), aluminum nitrate (Al(NO₃)₃), chromium acetate(Cr(CH₃COO)₃), chromium nitrate (Cr(NO₃)₃), chromium sulfate(Cr₂(SO₄)₃), and chromium oxalate (Cr₂(C₂O₄)₃). Less preferred examplesof metals would include any compound that contains a metal with a formalcharge greater than 1. If the metal salt forms an insoluble complex witha monomer, it will be preferred to add the metal during or afterpolymerization.

In the preferred embodiment of this invention, one or more surfactantswill be present during the polymerization and with the dissolved orsuspended polymer. The surfactant will keep water-insoluble monomers insolution during polymerization, and later to keep the entire polymer insolution. Presently preferred are the non-ionic surfactants, such asthose with the structures CH₃(CH₂)_(n)CO(OCH₂CH₂)_(m)OH (such as, forexample, polyethylene oxide (14) monostearate,CH₃(CH₂)_(n)(OCH₂CH₂)_(m)OH, and those with trade names that include“Tween”, or “Triton”.

It is also possible to add additional monomers into the polymer. Thesemonomers may act as dyes, pH indicators, softeners, compounds that wouldgive the fibrous substrate resistance to fungi or bacteria, spacers tomake the polymer more flexible, components to increase the solubility ofthe polymer in a carrier solvent system (e.g., mixtures of water, polarorganic solvents, and surfactants) from which the polymer is depositedonto the fibrous substrates, or components (non-fluorinated) that addhydrophobicity. Such monomers are known to those of skill in the art.Examples of potential softeners that could soften the polymer and arecommercially available include acrylic acid and methacrylic acid estersof alkyl chains or siloxane oligomers or polymers.

In a presently preferred embodiment, the treatment is selected fromrandom copolymers consisting of a fluoroacrylate (e.g., FX-13, 3M; orZonyl TA-N, DuPont) containing at least two carboxyl-containingmonomers, e.g., acrylic acid, per molecule, some vinylidene chloride,and/or PEG-acrylate, and the metal salt is ZrO(NO₃)₂. The metal salt andthe fluoropolymer are added from an aqueous solution to the keratinousfabric in the normal manner (e.g., padding on of an aqueous solutioncontaining the salt and the polymer, followed by drying at 90° C. to175° C. for about 30 seconds to about 5 min). Without being limited bytheory, it is believed that the zirconium salt complexes with carboxylor carboxylate groups from aspartic acid and glutamic acid residues inthe keratinous substrate while at the same time it reacts with thecarboxyl-containing polymer, thus serving as a coordination bridgebetween the wool and the water/soil resistant polymer. The polymer maybe linked by one or multiple carboxyls to the wool through the metal.Alternatively, the polymer may be crosslinked to itself and to otherpolymer chains by the mordant. It may also be that the mordant does notbind the polymer to the wool, but rather simply renders the polymerinsoluble.

This invention is further directed to a diblock copolymer that containsone or more blocks of an acidic monomer, such as acrylic acid, alongwith one or more blocks of fluorinated monomers. This polymer is usefulto coat fabrics using a metal. In a presently preferred embodiment, thehydrophilic monomers are concentrated to one end of the macromolecule.It is believed that this will increase its water solubility and improveits ability to bind to fabrics.

The synthesis of the copolymer comprises the steps of:

1) Polymerizing FX-13, Zonyl TA-N, or another monomer that does notcontain a carboxyl group in the presence of a chain transfer agent thatcontains a sulfhydryl group and an amine group, one example being, butthe invention not limited to, HS(CH₂)_(n)NH₂ (where n=2-20). Twocommercially available compounds that have amino and thiol groups are1-amino-2-methyl-2-propanethiol (sold by Aldrich as the hydrochloride)and 2-(butylamino)ethanethiol.

2) Reacting the amine-terminated polymer produced in Step 1) with acompound (such as N-acetyl homocysteine thiolactone or 2-iminothiolane,for example) that will convert the amine-terminated polymer into asulfhydryl-terminated polymer.

3) Performing a polymerization in the presence of thesulfhydryl-terminated polymer produced in Step 2) with a monomerdifferent from the monomer used in Step 1). Thus, thesulfhydryl-terminated polymer generated in Step 2) acts as a chaintransfer agent for the polymer created in Step 3) and caps it, creatinga block copolymer.

A graft copolymer may be made, where the grafted portion is eithercarboxyl groups or fluorinated material or another material, such asmetal-containing monomers or oligomers. It is also possible to make apolymer using some or all of monomers that are themselves oligomers.

The present invention is further directed to the yarns, fibers, fabrics,webs, finished goods, or other textiles (encompassed herein under theterms “textiles” and “fibrous substrates”) treated with the permanent orsubstantially durable water/soil-resistant fluoropolymer. These fibroussubstrates will display comparable textile performance of the untreatedtextile or other substrate without the wetting/staining of traditionaltextiles.

These fibrous substrates can be used in a variety of ways including, butnot limited to various articles of clothing, including informalgarments, daily wear, workwear, activewear and sportswear, especiallythose for, but not limited to easily wet or stained clothing, such asformal garments, coats, hats, shirts, pants, gloves, and the like; otherfibrous substrates subject to wetting or staining, such as interiorfurnishings and upholstery therefor, carpets, awnings, draperies,upholstery for outdoor furniture, protective covers for barbecues andoutdoor furniture, automotive and recreational vehicle upholstery, sailsfor boats, and the like; and industrial uses, such as those listed inAdanur, S., Wellington Sears Handbook of Industrial Textiles, pp. 8-11(Technomic Publishing Co., Lancaster, Pa., 1995).

The durable water/soil-resistant webs of the present invention areintended to include fabrics and textiles, and may be a sheet-likestructure (woven, knitted, tufted, stitch-bonded, or non-woven)comprised of fibers or structural elements. Included with the fibers canbe non-fibrous elements, such as particulate fillers, binders, sizes,and the like. The fibrous substrates include fibers, woven and non-wovenfabrics derived from natural or synthetic fibers or blends of suchfibers, as well as cellulose-based papers, and the like. They cancomprise fibers in the form of continuous or discontinuousmonofilaments, multifilaments, staple fibers, and yarns containing suchfilaments and/or fibers, which fibers can be of any desired composition.The fibers can be of natural, manmade, or synthetic origin. Mixtures ofnatural fibers, manmade fibers, and synthetic fibers can also be used.Examples of natural fibers include cotton, wool, silk, jute, linen, andthe like. Examples of man-made fibers include regenerated celluloserayon, cellulose acetate and regenerated proteins. Examples of syntheticfibers include polyesters (including polyethyleneterephthalate andpolypropyleneterephthalate), polyamides (including nylon), acrylics,olefins, aramids, azlons, modacrylics, novoloids, nytrils, aramids,spandex, vinyl polymers and copolymers, vinal, vinyon, Kevlar®, and thelike.

To prepare the durable water/soil-resistant webs, the fiber, the yarn,the fabric, or the finished good is exposed (by methods known in the artsuch as by soaking, spraying, dipping, fluid-flow, padding, and thelike) to the metal salt and to the water/soil-resistant fluoropolymer,each of which has been dissolved, suspended, or emulsified in an aqueoussolution in either a one-step or a two-step process. Thetextile-reactive metals of the metal salts may react with the web bycoordinate bonding and the water/soil-resistant polymer reacts with themetals, by coordinate bonding, to permanently attach to the web.Alternatively, upon drying, the metals may crosslink the polymer chainsto form an insoluble compound that is non-covalently bound to the web.The treated web is then removed from the solution, dried, and cured.

The invention is further directed, in a presently preferred embodimentto the process for treating fibrous substrates with water/soil repellentcoatings durable to repeated cleanings, wherein the polymer and themetal of the coating are applied to the fiber, yarn, or textilesimultaneously, that is, in a one-step process. This greatly increasesthe efficiency of the treatment because of cost savings of chemicals andequipment time. The metal salt and the fluoropolymer are mixed togetherin an aqueous solution and the fiber, the yarn, the fabric, or thefinished good is exposed simultaneously to both, by methods known in theart such as by soaking, spraying, dipping, fluid-flow, padding, and thelike. The treated web is then removed from the solution, dried, and, ifdesired, cured.

In another, two-step process for preparing the permanent water/soilresistant webs, the fiber, the yarn, the fabric, or the finished good isexposed to the metal salt dissolved or suspended in an aqueous solution.The textile-reactive metals of the metal salts may react with the web bycoordinate bonding. The article is then dried, followed by exposure tothe permanent water/soil resistant fluoropolymer suspended in an aqueoussolution by methods known in the art such as by soaking, spraying,dipping, fluid-flow, padding, and the like. The water/soil resistantpolymer reacts with the metals on the web, by coordinate bonding, topermanently attach to the web. The treated web is then removed from thesolution, dried, and cured.

When the process is carried out in one step, it is essential thatneither the concentration of the metal, nor the concentration of thegroup that the metal complexes with be so high as to cause precipitationof the suspended or dissolved polymer. It is also essential that enoughmetal atoms and metal-complexing groups be present to cause the polymerto be insoluble or substantially insoluble in solvents such as water andtetrachloroethylene, which are used to clean textiles, after the polymerhas been dried or cured on a textile. The actual concentrations of themetals and the complexing groups will depend both on the amount ofsurfactant that may be present in the solution as well as on the numberof other polar groups that may be present on the polymer. Suchconcentrations can be determined by one of skill in the art followingstandard procedures without undue experimentation.

In the processes of the invention, the concentration of the metal saltin solution can be from about 0.05M to about 1M, preferably from about0.1M to about 0.4M, more preferably about 0.25M; depending, however, onthe characteristics of the particular web to be treated and theparticular water/soil resistant fluoropolymer to be attached.

The concentration of the water/soil resistant fluoropolymer in solutioncan be from about 0.1% to about 25%, preferably from about 1% to about5%, more preferably about 2.5%; depending, however, on thecharacteristics of the particular permanent water/soil resistant polymerselected (such as molecular weight or material). The ratio offluorinated monomer to acidic monomer can vary from about 1:0.75 toabout 1:5, preferably from about 1:2.5 to about 1:4, more preferablyabout 1:3.

The process temperature for either the one- or 2-step process can varywidely, depending on the affinity of the salt for the fibrous substrateand for the water/soil resistant fluoropolymer. However, the temperatureshould not be so high as to decompose the reactants or so low as tocause inhibition of the reaction or freezing of the solvent. Unlessspecified to the contrary, the processes described herein take place atatmospheric pressure over a temperature range from ambient temperatureto an elevated temperature that is below the boiling point of thesolvent used, preferably from about 10° C. to about 110° C., morepreferably from about 20° C. to about 60° C., and most preferably at 20°C. Conveniently, the processes will be at ambient temperature. The timerequired for the processes herein will depend to a large extent on thetemperature being used and the relative reactivities of the startingmaterials. Therefore, the time of exposure of the fibrous substrate tothe metal salt and the polymer in solution can vary greatly, for examplefrom about a few seconds to about two hours. Normally, the exposure timewill be from a few seconds to ten minutes. Drying is carried out atambient temperature or at a temperature above ambient, up to about 220°C. The pH of the solution will be dependent on the fibrous substratebeing treated. For example, the pH should be kept at neutral to acid orperhaps mildly basic when treating wool, because wool will degrade instrong base, whereas when treating cotton the pH should be kept atmildly acidic to neutral to basic, keeping in mind that metal saltsoften are insoluble in alkali. However, the solution pH's will probablynot be too critical when the fibrous substrate is exposed for only abrief time and if the curing temperature is not too high. Additionally,the deposition of water/soil-resistant polymer with charged groups(e.g., carboxylates, sulfonates, and the like) is expected to bedependent on solution pH. Salts (such as, for example, NaCl, Na₂SO₄,etc.) may optionally be added to increase the rate of adsorption ofanionic polymers onto the fibers. Unless otherwise specified, theprocess times and conditions are intended to be approximate.

EXAMPLES Example 1

3.603 Grams of acrylic acid, 8.931 g FX-13 (3M), 0.106 g AIBN, and 0.483g mercaptosuccinic acid were dissolved in 29.565 g THF. While stirring,the reaction vessel was purged with nitrogen for a few minutes. Themixture was then heated and held at reflux for 16 hours. The THF/polymersolution may either be used directly or the THF may be removed by rotaryevaporation, leaving the “20-mer” polymer behind.

Example 2

A 0.232 M solution of ZrO(NO₃)₂ in 95% water/5% isobutanol was paddedonto wool. The wool was then dried at 90° C. Next, a solution of 1.76 gfluoropolymer (4 parts acrylic acid, 1 part FX-13, 1% mercaptosuccinicacid, “100-mer”; prepared following the procedure of Example 1) at pH6.9 in 95% water/5% isobutanol was padded onto wool. The wool was againdried at 90° C. The material was then rinsed for 3 minutes under flowingtap water and dried in the oven at 90° C. The sample was immersed(overnight) in a stirred vessel containing tetrachloroethylene to testthe stability of the coating. It was then removed and allowed to dry inthe air.

Test for repellency showed that dodecane, water, and an 81%methanol/water mixture beaded up on the surface. Decane wet it.

Example 3

64 Grams of Zonyl TA-N (a fluorochemical acrylate from DuPont), 18 gstearyl acrylate, 15 g polyethylene glycol monoacrylate (Aldrich,M_(n)˜375), 3 g calcium acrylate, 0.5 g dodecanethiol, 8 g POE(14)monostearate, 1 g 2,2′-azobis(2-methylpropionamidine) dihydrochloride,100 g isopropyl alcohol, and 100 g water were homogenized. The calciumacrylate was dissolved in water before it was added. The mixture wasthen homogenized and heated under nitrogen to 70-80° C. for about 2 hr.This solution was diluted to 20% of its original concentration withwater and applied to wool (Burlington Industries 8823 tan wool). Thewool was padded to ˜100% wet pickup and dried and cured in an oven for18 min. The temperature in the oven rose during this period from 105° C.to 140° C. The water and oil repellencies of these samples were thenmeasured both before and after immersion in rapidly-stirredtetrachloroethylene (TCE). The following Table gives the oil repellencyas measured by the AATCC test method (see below) as a function of time.

Hours in TCE 0 1 1.5 2 4 16.2 18 AATCC 7.33 6.66 6.66 7.0 6.66 6.33 6.33RatingOil Repellency Measurement

The oil repellency (OR) of a treated substrate is measured by theAmerican Association of Textile Chemists and Colorists (AATCC) StandardTest Method No. 118-1983, which test is based on the resistance oftreated substrate to penetration by oils of varying surface tensions.Treated substrates resistant only to Nujol.RTM mineral oil (the leastpenetrating of the test oils) are given a rating of 1, whereas treatedsubstrates resistant to heptane (the most penetrating of the test oils)are given a rating of 8. Other intermediate values are determined by useof other pure oils or mixtures of oils, as shown in the following Table.

Standard Test Liquids AATCC Oil Repellency Rating Number Composition 1Nujol.RTM 2 Nujol.RTM/n-Hexadecane (65/35) 3 n-Hexadecane 4n-Tetradecane 5 n-Dodecane 6 n-Decane 7 n-Octane 8 n-Heptane

1. A copolymer comprising i) an acid-containing monomer, ii) ametal-containing monomer, and iii) a fluorinated monomer, said copolymerincorporating metal atoms with a formal charge of 2 or greater.
 2. Acopolymer according to claim 1 wherein said fluorinated monomer has thestructure:

wherein: m is 0 to 2; n is 0 or 1; o is 1 or 2; A is —SO₂—, —N(W)—SO₂—,—CONH—, —CH₂—, or —CF₂—; R is a linear, branched, or cyclic fully- orpartially-fluorinated hydrocarbon; W is hydrogen or C₁-C₄ lower alkyl;and X is acrylate (H₂C═CHCO₂—), methacrylate (H₂C═C(CH₃)CO₂—), or acarbon—carbon double bond (H₂C═CH—).
 3. A copolymer according to claim 1wherein said metal-containing monomer is selected from the groupconsisting of calcium acrylate, magnesium acrylate, aluminum acrylate,chromium acrylate, calcium styrene sulfonate, magnesium styrenesulfonate, aluminum styrene sulfonate, and chromium styrene sulfonate.4. A copolymer according to claim 1 wherein said acid-containing monomeris selected from the group consisting of acrylic acid, methacrylic acid,maleic anhydride, maleic acid, crotonic acid, itaconic acid, andmixtures thereof.
 5. A copolymer according to claim 1 wherein saidcopolymer comprises at least one block of said acid-containing monomersand at least one block of said fluorinated monomers.
 6. A copolymeraccording to claim 1 wherein said copolymer comprises at least one blockof hydrophilic monomers, which hydrophilic monomers are concentrated toone end of the copolymer.
 7. A copolymer comprising i) anacid-containing monomer or an acid-containing monomer precomplexed withmetal atoms having a formal charge of 2 or greater, and ii) afluorinated monomer, said copolymer having reactive groups that cancoordinately bind with metal atoms having a formal charge of 2 orgreater if the metal atom is not already precomplexed in theacid-containing monomer.
 8. A copolymer according to claim 7 whereinsaid fluorinated monomer has the structure:

wherein: m is 0 to 2; n is 0 or 1; o is 1 or 2; A is —SO₂—, —N(W)—SO₂—,—CONH—, —CH₂—, or —CF₂—; R is a linear, branched, or cyclic fully- orpartially-fluorinated hydrocarbon; W is hydrogen or C₁-C₄ lower alkyl;and X is acrylate (H₂C═CHCO₂—), methacrylate (H₂C═C(CH₃)CO₂—), or acarbon—carbon double bond (H₂C═CH—).
 9. A copolymer according to claim 7wherein said acid-containing monomer is selected from the groupconsisting of acrylic acid, methacrylic acid, maleic anhydride, maleicacid, crotonic acid, itaconic acid, and mixtures thereof.
 10. Acopolymer according to claim 7 wherein said copolymer is a diblockcopolymer comprising at least one block of said acid-containing monomersand at least one block of said fluorinated monomers.
 11. A copolymeraccording to claim 7 wherein said copolymer is a diblock copolymercomprising at least one block of hydrophilic monomers, which hydrophilicmonomers are concentrated to one end of the copolymer.